JP2510647B2 - Method for immobilizing chemically reactive agents on the surface of synthetic resin particles - Google Patents

Method for immobilizing chemically reactive agents on the surface of synthetic resin particles

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Publication number
JP2510647B2
JP2510647B2 JP63004632A JP463288A JP2510647B2 JP 2510647 B2 JP2510647 B2 JP 2510647B2 JP 63004632 A JP63004632 A JP 63004632A JP 463288 A JP463288 A JP 463288A JP 2510647 B2 JP2510647 B2 JP 2510647B2
Authority
JP
Japan
Prior art keywords
batch
resin particles
reactive agent
chemically reactive
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
JP63004632A
Other languages
Japanese (ja)
Other versions
JPS63191834A (en
Inventor
ピー・グプタ ベッド
イー．ヘーガー ジェローム
エー．ノーブル ラルフ
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SHINAAJISUTEIKUSU IND Ltd
Original Assignee
SHINAAJISUTEIKUSU IND Ltd
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Filing date
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Application filed by SHINAAJISUTEIKUSU IND Ltd filed Critical SHINAAJISUTEIKUSU IND Ltd
Publication of JPS63191834A publication Critical patent/JPS63191834A/en
Application granted granted Critical
Publication of JP2510647B2 publication Critical patent/JP2510647B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/005—Methods for mixing in batches
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/20—Measuring; Control or regulation
    • B01F35/22—Control or regulation
    • B01F35/221—Control or regulation of operational parameters, e.g. level of material in the mixer, temperature or pressure
    • B01F35/2214—Speed during the operation
    • B01F35/22142—Speed of the mixing device during the operation
    • B01F35/221421—Linear speed of the tip of a moving stirrer during the operation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/20—Measuring; Control or regulation
    • B01F35/22—Control or regulation
    • B01F35/221—Control or regulation of operational parameters, e.g. level of material in the mixer, temperature or pressure
    • B01F35/2215—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
    • B29B7/06—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices
    • B29B7/10—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary
    • B29B7/12—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with single shaft
    • B29B7/16—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with single shaft with paddles or arms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/82—Heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/203—Solid polymers with solid and/or liquid additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2055/00—Use of specific polymers obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of main groups B29K2023/00 - B29K2049/00, e.g. having a vinyl group, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2055/00—Use of specific polymers obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of main groups B29K2023/00 - B29K2049/00, e.g. having a vinyl group, as moulding material
    • B29K2055/02—ABS polymers, i.e. acrylonitrile-butadiene-styrene polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0014—Catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/25—Solid
    • B29K2105/251—Particles, powder or granules
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2998—Coated including synthetic resin or polymer

Description

【発明の詳細な説明】 （産業上の利用分野） 本発明は適当な合成樹脂へ化学的反応性作用剤（chem
ically reactive agents）を適用することに関する。よ
り具体的には、本発明は化学的反応性作用剤を合成樹脂
粒子表面に固定又は固着（lock）させることによって、
熱可塑性プラスチック製品又は熱硬化性プラスチック製
品に成形出来る合成樹脂粒子を製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION Industrial Field of the Invention The present invention relates to chemically reactive agents (chem) to suitable synthetic resins.
Applying ically reactive agents). More specifically, the present invention provides a chemically reactive agent by immobilizing or locking the surface of synthetic resin particles,
The present invention relates to a method for producing synthetic resin particles that can be molded into thermoplastic or thermosetting plastic products.

（従来技術） 合成樹脂の溶融化又は流動化（fluxing）中に、例え
ば架橋剤（cross linking agents）や化学発泡剤等の化
学的反応性作用剤を混合することが行なわれている。あ
る種の合成樹脂と共に用いられる架橋剤の例として、ハ
ーキュリーズ社（Hercules Inc.）が商標名DI−CUPにて
販売する過酸化ジクミルや、商標名VUL−CUPにて販売す
る活性度の高い過酸化物等が挙げられる。化学的発泡剤
の例として、商標名CELOGEN（アゾジカーボンアミド、
パラ、パラ−オキシ ビス−（ベンゼンスルホンヒドラ
ジド）及びパラ−トルエンスルホニルセミカルバジド）
等が挙げられる。その他の化学的反応性作用剤として、
グラフト剤を挙げることが出来、このグラフト剤はある
種の樹脂と共に用いることが出来る。多くの場合、化学
的反応性作用剤が所定の温度に達すると化学反応を生ず
るが、このためには樹脂の流動化温度（fluxing temper
ature）よりも高い温度にせねばならない。(Prior Art) During melting or fluxing of a synthetic resin, a chemically reactive agent such as a cross linking agent or a chemical blowing agent is mixed. Examples of cross-linking agents used with certain synthetic resins include dicumyl peroxide sold under the trade name DI-CUP by Hercules Inc. and highly active peroxide sold under the trade name VUL-CUP. Examples thereof include oxides. As an example of a chemical blowing agent, the trade name CELOGEN (azodicarbonamide,
Para, para-oxybis- (benzenesulfone hydrazide) and para-toluenesulfonyl semicarbazide)
Etc. As other chemically reactive agents,
There may be mentioned a grafting agent, and this grafting agent can be used together with a certain resin. In many cases, the chemically reactive agent undergoes a chemical reaction when it reaches a certain temperature, which is due to the fluxing temperature of the resin.
ature).

本発明の中で言及する合成樹脂の種類には、線状及び
分岐低密度ポリエチレン、中密度ポリエチレン、高密度
ポリエチレン並びにポリエチレンの共重合体が含まれ
る。その他の適当な樹脂として、ポリ塩化ビニル、ポリ
塩化ビニル共重合体、ポリプロピレン、ポリプロピレン
共重合体、ポリスチレン、アクリル樹脂、エチレンビニ
ルアルコール、高分子重量ワックス、アクリロニトリル
−ブタジエン−スチレン共重合体、ポリ塩化ビニリデ
ン、ポリ塩化ビニリデン共重合体及びこれ等の適当な混
合物が挙げられる。The types of synthetic resins referred to in the present invention include linear and branched low density polyethylene, medium density polyethylene, high density polyethylene and copolymers of polyethylene. Other suitable resins include polyvinyl chloride, polyvinyl chloride copolymer, polypropylene, polypropylene copolymer, polystyrene, acrylic resin, ethylene vinyl alcohol, high molecular weight wax, acrylonitrile-butadiene-styrene copolymer, polychlorinated resin. Included are vinylidene, polyvinylidene chloride copolymers and suitable mixtures thereof.

更に安定剤、潤滑剤、充填剤及び二酸化チタンのよう
な改質剤（modifiers）等のその他成分を、化学的反応
性作用剤の投入前又は投入時に樹脂に添加することも出
来る。In addition, other components such as stabilizers, lubricants, fillers and modifiers such as titanium dioxide can be added to the resin before or during the addition of the chemically reactive agent.

多くのポリマー樹脂は、本来的に粉末（powder）、細
粒（granule）又はフレーク状に生ずる。幾つかの樹脂
は本来的にペレット形状にて生ずる。粉末は粒子サイズ
が200メッシュよりも小さく、細粒は粒子サイズが約35
〜45メッシュの範囲内、ペレットは長さ約0.3cmと定義
される。本発明の目的を達成するためには、樹脂粒子は
粉末又は細粒又はフレーク形状であるのが望ましい。し
かし乍ら、樹脂粒子がペレット状であったり、又は反応
性作用剤を粒子に固定させるには大き過ぎる場合でも、
これ等のより大きな粒子は粉挽きすることによりサイズ
を小さくして微細な粒子にすることが出来る。本明細書
中で用いられる「微細な粒子（finely divided particl
es）」という用語には、粉末及びフレークを含み、一般
的には粒子のメッシュサイズは約10以下である。Many polymeric resins naturally occur in powders, granules or flakes. Some resins naturally occur in pellet form. The powder has a particle size smaller than 200 mesh, and the fine particles have a particle size of about 35.
Within the range of ~ 45 mesh, pellets are defined as about 0.3 cm in length. In order to achieve the object of the present invention, it is desirable that the resin particles are in the form of powder or fine particles or flakes. However, even if the resin particles are in the form of pellets or are too large to fix the reactive agent to the particles,
These larger particles can be ground to a finer size by grinding. As used herein, "finely divided particl"
The term "es)" includes powders and flakes, and generally the particles have a mesh size of about 10 or less.

従来の多くの方法では、反応性作用剤をミキサーの中
で樹脂と混合させるには、少なくとも溶融が部分的に生
ずる温度にて行なわなければならない。これは、発泡剤
をポリ塩化ビニルの粉末と共に用いる時はそうではな
い。しかし乍ら、混合温度は作用剤の反応温度以下に保
たれる。多くの樹脂の場合、当初の形態が大きい粒子で
あれ小さな粒子であれ、コンパウンドの製造者は、製品
をブレンドし、溶かし（flux）、ペレタイジングを行な
う。そして、この工程から得た製品をペレット状にて出
荷するか、或は最終製品とする前に粉挽きして粉末にす
るのである。最終工程には、第２の溶融工程を含んでお
り、反応性作用剤はこの時に活性化される。伝統的なPV
C粉末コンパウンドの場合、活性成分をPVC樹脂粒子に結
合させるのに特別な工夫を要しないが、それを除いた場
合、従来の技術では２回の溶融工程を必要とし、その工
程の間にはペレタイジング工程と粉挽き工程を必要とす
る。本発明の１つの目的は、１回の溶融工程によって同
等若しくはそれ以上の特性を備えた製品を作り出すこと
にある。In many conventional methods, the reactive agent must be mixed with the resin in the mixer at least at a temperature at which melting occurs. This is not the case when using blowing agents with polyvinyl chloride powder. However, the mixing temperature is kept below the reaction temperature of the agent. For many resins, the compound manufacturer, whether large or small in initial morphology, blends, fluxes, and pelletizes the product. Then, the product obtained from this step is shipped in the form of pellets, or ground into a powder before the final product. The final step involves a second melting step, at which time the reactive agent is activated. Traditional PV
In the case of C powder compound, no special device is required to bind the active ingredient to the PVC resin particles, but if it is excluded, the conventional technique requires two melting steps, and between the steps, Requires pelletizing and milling steps. One object of the present invention is to produce a product with equivalent or better properties in a single melting step.

（発明が解決しようとする課題） 本発明は、化学的反応性作用剤の合成樹脂粒子への固
定を、樹脂全体に溶融することなく行なえる方法を提供
することを目的としている。本明細書の中で使用する
「固着（lock）」という用語は、反応性作用剤を樹脂粒
子表面へ通常の材料取り扱いでは外れない程度にしっか
りと結合させることを意味する。本発明は、更に又、混
合温度を反応性作用剤の分解温度よりも可成り低い温度
に維持しながら、化学的反応性作用剤を合成樹脂粒子表
面に固着させることを目的としている。本発明は更に
又、化学的反応性作用剤を粒子の表面に固着させた粒子
状の中間樹脂製品を提供することを目的としている。こ
のように、樹脂を溶融せず、又この種の既存製品に於け
るような高い温度の加熱を行なわない製品を提供するこ
とが出来る。(Problems to be Solved by the Invention) An object of the present invention is to provide a method capable of fixing a chemically reactive agent to synthetic resin particles without melting the entire resin. The term "lock" as used herein means to bind the reactive agent to the surface of the resin particles so tightly that they cannot be removed by normal material handling. The invention also aims at fixing the chemically reactive agent on the surface of the synthetic resin particles while maintaining the mixing temperature at a temperature well below the decomposition temperature of the reactive agent. Still another object of the present invention is to provide a particulate intermediate resin product having a chemically reactive agent adhered to the surface of the particles. In this way, it is possible to provide a product which does not melt the resin and which does not heat at a high temperature as in the existing products of this type.

この方法によってコンパウンド製造者は１つの溶融工
程を省くことが出来るから、早期反応が起こることもな
く、高品質の分散物を得ることが出来る。これによって
混合工程に必要なエネルギーを少なくして製造コストを
下げることが出来、ペレタイジング又は粉挽きも必要と
しない。This method allows the compound manufacturer to dispense with one melting step and thus obtain a high quality dispersion without premature reaction. This allows less energy to be used in the mixing process to reduce manufacturing costs and does not require pelletizing or grinding.

コンパウンド製造者が顧客に販売する中間製品は、射
出成形、粉末コーティング、回転成形、押出し加工、そ
の他の成形技術に適している。The intermediate products that compound manufacturers sell to their customers are suitable for injection molding, powder coating, rotomolding, extrusion and other molding techniques.

（課題を解決するための手段） 適当な合成樹脂表面に化学的反応性作用剤を固着する
ための本発明の方法は次の工程から構成される。(Means for Solving the Problems) The method of the present invention for fixing a chemically reactive agent on the surface of a suitable synthetic resin comprises the following steps.

微細な樹脂粒子の１バッチ（one batch）を密閉した
混合室の中で化学的反応性作用剤と共に激しく混合して
熱運動学的に加熱する。なお、混合室には複数のブレー
ドが配備され、該ブレードは混合室内の中心軸の廻りを
回転するアームに固定され、ブレードの先端部での速
度、即ちブレードチップ速度（blade tip speed）は毎
秒約18m以上である。次に化学的反応性作用剤が樹脂粒
子表面に固着されるまで、１分以内の時間でバッチを混
合する。この時、バッチの温度は、反応性作用剤の分解
温度よりもかなり低く、樹脂粒子の溶融温度よりも低い
温度に保たれる。その後、バッチを混合室から取り出
し、次にこれを冷却して樹脂粒子の凝集を防止する。One batch of fine resin particles is vigorously mixed and thermokinetically heated with a chemically reactive agent in a closed mixing chamber. Incidentally, a plurality of blades are provided in the mixing chamber, the blades are fixed to an arm that rotates around the central axis in the mixing chamber, and the speed at the tip of the blade, that is, the blade tip speed, is every second. It is about 18m or more. The batch is then mixed within 1 minute until the chemically reactive agent is attached to the resin particle surface. At this time, the temperature of the batch is maintained at a temperature considerably lower than the decomposition temperature of the reactive agent and lower than the melting temperature of the resin particles. The batch is then removed from the mixing chamber and then cooled to prevent resin particle agglomeration.

望ましい実施態様では、樹脂はポリエチレン又はポリ
エチレン共重合体であり、バッチの排出温度は105℃以
下であり、取り出されたバッチはリボンブレンダ又はそ
の他適当な設備の中で冷却される。化学的反応性作用剤
の第１の例として架橋剤が挙げられ、第２の例として化
学的発泡剤を挙げることが出来る。In a preferred embodiment, the resin is polyethylene or a polyethylene copolymer, the discharge temperature of the batch is below 105 ° C, and the withdrawn batch is cooled in a ribbon blender or other suitable equipment. A first example of the chemically reactive agent is a crosslinking agent, and a second example is a chemical foaming agent.

本発明の方法に使用する原材料は、樹脂を細かく砕い
た微細な粒子である。合成樹脂の粒子は本来的な発生形
態、即ち未加工の形態であることが望ましいが、未加工
形態の材料の粒子が大きい場合、細かく粉砕せねばなら
ない。そうしないと、分散したとき、有効な活性成分を
受け入れる表面積が不十分となるためである。粒子のメ
ッシュサイズは10を超えないことが望ましい。強力混合
工程の前に、化学的反応性作用剤を、樹脂粒子と予めブ
レンドしてもよい。必要に応じて、その他の組成物を化
学的反応性作用剤と同時に添加することも出来る。樹脂
粒子と化学的反応性作用剤の１バッチを非常に強力なミ
キサー（例えば、Goeser氏に付与された米国特許第3266
738号に開示されたものが挙げられる）の中に入れる。
この特許は非常に強力なミキサーについて記載してお
り、該ミキサーには複数のブレードが設けられ、該ブレ
ードは封入室内の軸の廻りを回転する。米国特許第4230
615号には、ミキサーの温度とは別に、ミキサー内のバ
ッチ温度をモニターし、次にバッチが所定温度に到達し
たとき、当該バッチをミキサーから取り出す装置を開示
している。The raw material used in the method of the present invention is fine particles obtained by finely crushing a resin. It is desirable that the particles of the synthetic resin are in the original generation form, that is, the unprocessed form, but if the particles of the material in the unprocessed form are large, they must be finely ground. Otherwise, when dispersed, there will be insufficient surface area to receive the active ingredient. It is desirable that the mesh size of the particles does not exceed 10. The chemically reactive agent may be pre-blended with the resin particles prior to the intensive mixing step. If desired, other compositions can be added simultaneously with the chemically reactive agent. A batch of resin particles and a chemically reactive agent is mixed with a very powerful mixer (eg, US Pat. No. 3,266,266 to Goeser).
738).
This patent describes a very powerful mixer, which is provided with a plurality of blades which rotate about an axis in the containment chamber. U.S. Pat.No. 4230
No. 615 discloses a device for monitoring the temperature of the batch in the mixer separately from the temperature of the mixer and then removing the batch from the mixer when the batch reaches a predetermined temperature.

混合工程は、第１図に示すような種類の非常に強力な
ミキサーの中で行う。第１図に示すミキサー（10）は囲
いのある混合室（11）を備え、該混合室は軸（14）に突
設したアーム（13）上で回転するブレード（12）を備え
ている。ブレード（12）は、表面積を可成り大きくし、
樹脂粒子にインパクトを与えるための櫂（かい）として
作用するようにしている。従って、ミキサーは樹脂粒子
にインパクトを与えるブレードを回転させるのに大馬力
のモータを必要とする。その他の種類のミキサーの中
に、ここに開示した強力ミキサーと同じように、インペ
ラーの先端部での速度が高速のものもあるが、これ等の
ミキサーはブレードの表面積は大きくなく、大馬力のモ
ータを必要としない。それ故、他のミキサーでバッチを
加熱すると、最大加熱時間は一般的には１分を遥かに越
え、30分に達することすらある。組成物は供給ファンネ
ル（15）から導入され、該ファンネルからウォーム（1
6）によって混合室（11）に送られる。油圧シリンダー
（17）によって排出フラップ（18）を作動させ、混合室
（11）内の材料を排出する。The mixing process takes place in a very powerful mixer of the kind shown in FIG. The mixer (10) shown in FIG. 1 comprises an enclosed mixing chamber (11), which comprises a blade (12) rotating on an arm (13) projecting from a shaft (14). The blade (12) has a large surface area,
It is designed to act as a paddle for impacting the resin particles. Therefore, the mixer requires a high horsepower motor to rotate the blades that impact the resin particles. Some other types of mixers, like the powerful mixers disclosed here, have higher speeds at the tips of the impellers, but these mixers do not have large blade surface areas and are of high horsepower. No motor needed. Therefore, when the batch is heated with other mixers, the maximum heating time is generally well over 1 minute and can even reach 30 minutes. The composition is introduced from a feed funnel (15) from which the worm (1
6) sent to the mixing chamber (11). The discharge flap (18) is operated by the hydraulic cylinder (17) to discharge the material in the mixing chamber (11).

軸（14）は高速で回転し、ブレード（12）のチップ速
度が18m/秒以上の速度となるようにしている。なお、他
の実施態様に於て、チップ速度は45m/秒以上にすること
も出来る。場合によっては、チップ速度を更に速くする
ことも出来る。表面積が大きなブレードのチップ速度を
高速にすることにより、混合室内の樹脂粒子を強く混合
して熱運動学的に加熱することが出来る。チップ速度は
樹脂の種類やバッチ量に応じて変えることが出来る。１
回の混合工程で２種類以上の速度を採用することも出来
る。混合時間は約４乃至25秒のオーダが望ましく、又、
１分を越えるべきではない。さもなければ樹脂粒子は凝
集して塊を生ずるからである。The shaft (14) rotates at a high speed so that the tip speed of the blade (12) is 18 m / sec or more. In another embodiment, the tip speed can be set to 45 m / sec or more. In some cases, the chip speed can be further increased. By increasing the tip speed of the blade having a large surface area, it is possible to strongly mix the resin particles in the mixing chamber and heat them thermodynamically. The chip speed can be changed according to the type of resin and the batch amount. 1
It is also possible to employ more than one type of speed in one mixing step. Mixing time should be on the order of 4 to 25 seconds, and
Should not exceed 1 minute. Otherwise, the resin particles will agglomerate to form lumps.

望ましい実施態様に於て、ミキサー内のバッチ温度
は、バッチから直接に赤外線を測定することによって決
められるようにしている。このため、バッチ温度は混合
室（11）の本体又は混合ブレード（12）の中で生ずる温
度変化の影響を受けない。このような測定装置は米国特
許第4230615号に開示されている。バッチ温度は排出の
瞬間をコントロール出来るように設定する。排出温度は
化学的反応性作用剤の分解温度よりも可成り低く、且つ
樹脂粒子の溶融温度よりも低く設定する。ブレードのチ
ップ速度を高速にすることによって、混合室内で樹脂粒
子がブレードに打たれたり、或は互いに衝突し合うこと
により、樹脂粒子の表面が加熱される。樹脂粒子の表面
は幾分柔らかくなり、作用剤が樹脂粒子に接着して固着
されるようになり、このため作用剤はミキサーの中で最
早移動できなくなる。作用剤は、粒子間に略均一に分散
されるようになる。混合室（11）内の回転ブレード（1
2）を高速にし、ブレードの表面積を大きくすることに
よって、バッチは、樹脂によっては10秒のオーダーにて
速やかに昇温する。このため、樹脂粒子の表面の熱は粒
子の中に伝わっていかず、粒子の凝集はおこらない。排
出時、幾つかの粒子は共に固着したり又は固着する傾向
にあり、これは表面が溶けたときに特に著しい。このた
め排出時には、より緩やかに粒子を混合しながら直ちに
冷却を施し、凝集を防止する。In the preferred embodiment, the batch temperature in the mixer is such that it can be determined by measuring infrared radiation directly from the batch. Therefore, the batch temperature is not affected by the temperature change occurring in the main body of the mixing chamber (11) or the mixing blade (12). Such a measuring device is disclosed in US Pat. No. 4,230,615. The batch temperature is set so that the instant of discharge can be controlled. The discharge temperature is set to be considerably lower than the decomposition temperature of the chemically reactive agent and lower than the melting temperature of the resin particles. By increasing the tip speed of the blade, the resin particles are hit against the blade in the mixing chamber or collide with each other, so that the surface of the resin particles is heated. The surface of the resin particles becomes somewhat softer and the agent becomes adhered and fixed to the resin particles, so that the agent can no longer move in the mixer. The agent becomes substantially evenly dispersed among the particles. Rotating blades (1) in mixing chamber (11)
By increasing the speed of 2) and increasing the surface area of the blade, the batch quickly heats up in the order of 10 seconds depending on the resin. Therefore, the heat on the surface of the resin particles is not transferred into the particles, and the particles do not aggregate. Upon ejection, some particles tend to stick together or tend to stick together, which is especially noticeable when the surface melts. Therefore, at the time of discharging, the particles are more gently mixed and immediately cooled to prevent agglomeration.

本発明の方法は、第２図に示す順序にて行なわれる。
化学的反応性作用剤を粒子に固着した後、ミキサーから
樹脂粒子を排出して、引き続き冷却する。粒子の凝集を
防止し、ケーキングを生ずることなく貯蔵できるように
するため、リボンミキサーのの中で行なうのが望まし
い。The method of the present invention is performed in the order shown in FIG.
After fixing the chemically reactive agent to the particles, the resin particles are discharged from the mixer and subsequently cooled. It is preferably done in a ribbon mixer to prevent particle agglomeration and to allow storage without caking.

ブレードのチップ速度が42m/秒の強力ミキサーの中に
線状及び分岐低密度ポリエチレン粒子を投入してテスト
を行なった。架橋させるための化学的反応性作用剤とし
て、活性の過酸化物であるVUL−CUPを用いた。この作用
剤の形態は、炭酸カルシウムのような不活性充填剤に分
散させた混合物のような場合がある。過酸化物の量は樹
脂の0.2〜16重量％の範囲内とするのが望ましい。VUL−
CUPの分解温度は149〜155℃の範囲内である。The tests were carried out by placing the linear and branched low density polyethylene particles in an intensive mixer with a blade tip speed of 42 m / sec. The active peroxide, VUL-CUP, was used as the chemically reactive agent for crosslinking. The form of this agent may be a mixture dispersed in an inert filler such as calcium carbonate. The amount of peroxide is preferably in the range of 0.2 to 16% by weight of the resin. VUL−
The decomposition temperature of CUP is in the range of 149-155 ° C.

混合室内のバッチ温度が90℃に達したときバッチを排
出した。この温度に到達するまでのバッチの混合時間は
約８〜10秒の範囲内であった。The batch was discharged when the batch temperature in the mixing chamber reached 90 ° C. The batch mixing time to reach this temperature was in the range of about 8-10 seconds.

第１表は、強力ミキサーの中で、過酸化物の架橋剤を
用いて粒状のLLDPEとLDPEを処理したときの試験結果を
示している。リボンブレンダーの中で酸化防止剤とポリ
エチレンを予め混合しておき、過酸化物を液状にして各
バッチに任意に添加した。Table 1 shows the test results when granular LLDPE and LDPE were treated with a peroxide crosslinker in an intensive mixer. The antioxidant and polyethylene were premixed in a ribbon blender to liquefy the peroxide and optionally added to each batch.

架橋剤を含有したこれ等のポリエチレン製品は、市販
のワイヤー及びケーブル製造装置を用いて、うまく押出
し加工することが出来、商業的使用を十分満足する特性
を備えた架橋ポリエチレン製絶縁ワイヤーを作ることが
出来た。These polyethylene products containing cross-linking agents can be successfully extruded using commercially available wire and cable making equipment to produce cross-linked polyethylene insulated wires with properties that are fully satisfactory for commercial use. Was completed.

試験はアゾ型発泡剤を粒状のLLDPEとLDPEに添加して
行なった。ポリエチレンに添加する発泡剤の比率を変え
て処理した。試験結果を第２表に示している。The test was conducted by adding an azo type foaming agent to granular LLDPE and LDPE. The treatment was performed by changing the ratio of the foaming agent added to polyethylene. The test results are shown in Table 2.

一組のテストの中で、発泡剤の量を樹脂の６重量％か
ら16重量％まで変えて行なった。潤滑剤と顔料を強力混
合工程を行なう前に添加した。両成分とも樹脂の２重量
％であった。強力ミキサーに投入するバッチ量は200〜2
50gであった。バッチ量は強力ミキサーの仕様に応じて
変えており、ミキサーの仕様が変わると、それに合わせ
てバッチ量は大きくしたり、小さくする。 In one set of tests, the amount of blowing agent was varied from 6% to 16% by weight of the resin. Lubricants and pigments were added before the intensive mixing process. Both components were 2% by weight of resin. 200 to 2 batches put into a powerful mixer
It was 50 g. The batch amount is changed according to the specifications of the powerful mixer, and when the specifications of the mixer are changed, the batch amount is increased or decreased according to the changes.

得られたポリエチレン製品は活性発泡作用剤が固定さ
れ、うまく押出し加工することが出来、商業的に満足し
うる形状を与えることが出来た。The resulting polyethylene product had the active foaming agent immobilized and could be successfully extruded to give a commercially acceptable shape.

強力ミキサーの処理温度は樹脂の溶融温度及び反応性
作用剤の分解温度に応じて変えることが出来る。The treatment temperature of the intensive mixer can be changed depending on the melting temperature of the resin and the decomposition temperature of the reactive agent.

バッチの温度を、作用剤の分解温度よりも可成り低く
すると共に、樹脂粒子の溶融温度よりも低い状態で、化
学的反応性作用剤を樹脂粒子に固定させることがキーで
ある。The key is to immobilize the chemically reactive agent on the resin particles while keeping the temperature of the batch considerably lower than the decomposition temperature of the agent and lower than the melting temperature of the resin particles.

処理後の冷却はリボンブレンダーの中で行なった。冷
却後、樹脂粒子の凝集やケーキングは起こらなかった。Cooling after the treatment was carried out in a ribbon blender. After cooling, agglomeration and caking of resin particles did not occur.

特許請求の範囲に規定された本発明の範囲から逸脱す
ることなく、開示した実施例に種々の変形を加えること
は出来る。Various modifications may be made to the disclosed embodiments without departing from the scope of the invention as defined by the claims.

【図面の簡単な説明】[Brief description of drawings]

第１図は強力ミキサーの側部断面図、及び第２図は本発
明に係る方法の工程を示すブロック図である。 （10）……ミキサー、（11）……混合室 （12）……ブレード、（13）……アーム （14）……軸、（17）……油圧シリンダー （18）……排出フラップFIG. 1 is a side sectional view of an intensive mixer, and FIG. 2 is a block diagram showing the steps of the method according to the present invention. (10) …… Mixer, (11) …… Mixing chamber (12) …… Blade, (13) …… Arm (14) …… Shaft, (17) …… Hydraulic cylinder (18) …… Discharge flap

───────────────────────────────────────────────────── フロントページの続き (72)発明者 ラルフ エー．ノーブル カナダ国 エム９ピー ３ティー７ オ ンタリオ，エトビコーク・メイプルブラ ンチ パス 77 (56)参考文献 特開 昭61−138663（ＪＰ，Ａ) 特開 昭55−104638（ＪＰ，Ａ) 日本粉体工業協会編「混合混練技術」 日本工業新聞社（昭和55年８月20日）第 133〜第136頁 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ralph A. Noble Canada M9 P3 Tee 7 Ontario, Etobicoke Maple Branch Pass 77 (56) References JP 61-138663 (JP, A) JP 55-104638 (JP, A) Japan Powder Industry “Mixing and kneading technology” edited by the association Nihon Kogyo Shimbun (August 20, 1980), pages 133-136

Claims (12)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】混合室に複数のブレードを配備し、該ブレ
ードは混合室内の中心軸の廻りを回転するアームに取り
付けられて先端部での速度が18m/秒以上での速度にて回
転しており、該混合室の中で微細な樹脂粒子のバッチを
化学的反応性作用剤と共に激しく混合して熱運動学的に
加熱し、 バッチの温度が反応性作用剤の分解温度よりも可成り低
く、樹脂粒子の溶融温度よりも低く維持できるように、
化学的反応性作用剤が樹脂粒子表面に固着するまで１分
以内の時間でバッチを混合し、 混合室からバッチを排出し、次いで 樹脂粒子同士が凝集するのを防止するため、排出したバ
ッチを冷却する 工程から構成されることを特徴とする化学的反応性作用
剤を合成樹脂粒子の表面に固着する方法。1. A plurality of blades are provided in a mixing chamber, and the blades are attached to an arm that rotates around a central axis in the mixing chamber and rotate at a speed of 18 m / sec or more at the tip. In this mixing chamber, a batch of fine resin particles is vigorously mixed with a chemically reactive agent and heated thermokinetically, and the temperature of the batch is much higher than the decomposition temperature of the reactive agent. Low, so that it can be kept below the melting temperature of the resin particles,
The batch is mixed within 1 minute until the chemically reactive agent adheres to the resin particle surface, the batch is discharged from the mixing chamber, and then the discharged batch is removed to prevent the resin particles from agglomerating. A method of fixing a chemically reactive agent to the surface of synthetic resin particles, which comprises a cooling step. 【請求項２】混合時間は４〜25秒の範囲内である特許請
求の範囲第１項に記載の方法。2. A method according to claim 1, wherein the mixing time is in the range of 4 to 25 seconds. 【請求項３】混合室内に於ける樹脂粒子のバッチと化学
的反応性作用剤の温度を測定し、所定温度に達したとき
バッチを排出する特許請求の範囲第１項に記載の方法。3. The method according to claim 1, wherein the temperature of the batch of resin particles and the chemically reactive agent in the mixing chamber is measured, and the batch is discharged when a predetermined temperature is reached. 【請求項４】樹脂はポリエチレン又はポリエチレン共重
合体である特許請求の範囲第２項に記載の方法。4. The method according to claim 2, wherein the resin is polyethylene or a polyethylene copolymer. 【請求項５】排出されたバッチはリボンブレンダーの中
で冷却する特許請求の範囲第１項に記載の方法。5. The method according to claim 1, wherein the discharged batch is cooled in a ribbon blender. 【請求項６】バッチの温度は微細な樹脂粒子の表面が軟
化する温度である特許請求の範囲第２項に記載の方法。6. The method according to claim 2, wherein the temperature of the batch is a temperature at which the surface of the fine resin particles is softened. 【請求項７】該合成樹脂は、線状及び分岐低密度ポリエ
チレン、中密度ポリエチレン、高密度ポリエチレン、エ
チレン共重合体、ポリプロピレン、プロピレン共重合
体、ポリ塩化ビニル、塩化ビニル共重合体、ポリスチレ
ン、アクリル樹脂、アクリルニトリルブタジエン−スチ
レン共重合体、ポリ塩化ビニリデン及び塩化ビニリデン
共重合体からなる群から選択される特許請求の範囲第１
項に記載の方法。7. The synthetic resin is a linear or branched low density polyethylene, medium density polyethylene, high density polyethylene, ethylene copolymer, polypropylene, propylene copolymer, polyvinyl chloride, vinyl chloride copolymer, polystyrene, Claim 1 selected from the group consisting of acrylic resin, acrylonitrile butadiene-styrene copolymer, polyvinylidene chloride and vinylidene chloride copolymer.
The method described in the section. 【請求項８】該化学的反応性作用剤が架橋剤である特許
請求の範囲第１項に記載の方法。8. The method according to claim 1, wherein the chemically reactive agent is a cross-linking agent. 【請求項９】該化学的反応性作用剤が化学発泡剤である
特許請求の範囲第１項に記載の方法。9. The method of claim 1 wherein said chemically reactive agent is a chemical blowing agent. 【請求項１０】該反応性作用剤が二種以上の組み合わせ
である特許請求の範囲第１項に記載の方法。10. The method according to claim 1, wherein the reactive agent is a combination of two or more kinds. 【請求項１１】反応性作用剤の一種又はその組合せが、
潤滑剤、処理酸又は安定剤のようなその他の添加剤と共
に用いられる特許請求の範囲第10項に記載の方法。11. A reactive agent or a combination thereof, comprising:
A method according to claim 10 for use with other additives such as lubricants, treating acids or stabilizers. 【請求項１２】特許請求の範囲第１項の方法により製造
され、化学的反応性作用剤が樹脂粒子の表面に固着した
微細な合成樹脂粒子。12. Fine synthetic resin particles produced by the method according to claim 1 and having a chemically reactive agent adhered to the surface of the resin particles.
JP63004632A 1987-01-12 1988-01-11 Method for immobilizing chemically reactive agents on the surface of synthetic resin particles Expired - Fee Related JP2510647B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US002,207 1979-01-09
US2,207 1987-01-12
US07/002,207 US4789597A (en) 1987-01-12 1987-01-12 Incorporation of chemically reactive agents on resin particles

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JPS63191834A JPS63191834A (en) 1988-08-09
JP2510647B2 true JP2510647B2 (en) 1996-06-26

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US4789597A (en) 1988-12-06
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DE3888546D1 (en) 1994-04-28
DE3888546T2 (en) 1994-06-30

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